CN113113598B - Water-based zinc-based nickel-cobalt battery positive electrode material and preparation method thereof - Google Patents

Water-based zinc-based nickel-cobalt battery positive electrode material and preparation method thereof Download PDF

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CN113113598B
CN113113598B CN202011434043.2A CN202011434043A CN113113598B CN 113113598 B CN113113598 B CN 113113598B CN 202011434043 A CN202011434043 A CN 202011434043A CN 113113598 B CN113113598 B CN 113113598B
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nickel
cobalt
zinc
phosphate
water
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CN113113598A (en
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孙小华
刘秋恒
李鸣
黄延清
陈善华
周琳翔
赵大福
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China Three Gorges University CTGU
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H01M10/38—Construction or manufacture
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

The invention discloses a water-based zinc-based nickel-cobalt anode material. The positive electrode material is nano flaky nickel cobalt phosphate which grows on a three-dimensional substrate, the negative electrode is a zinc sheet, and the electrolyte is potassium hydroxide with a certain concentration and soluble zinc salt aqueous solution. Compared with the prior art, the transition metal phosphate composite material is applied to a water system zinc-based nickel-cobalt battery system for the first time, and the nickel-cobalt phosphate prepared in situ on the foam nickel has a nano sheet structure with high specific surface area, has high specific capacity and good cycle stability, and is simple in preparation process and suitable for large-scale production.

Description

Water-based zinc-based nickel-cobalt battery positive electrode material and preparation method thereof
Technical Field
The invention belongs to the technical field of high-energy water-based batteries, and particularly relates to a high-energy water-based zinc-based nickel-cobalt battery anode material.
Background
With the progress of human society and the popularization of electronic devices and the vigorous popularization of low-carbon and environment-friendly electric traffic, the demand of secondary batteries for human beings is increasing. The secondary battery is a high-efficiency energy storage device, can realize repeated charge and discharge and recycling, and has the characteristics of small pollution, low cost and the like compared with the primary battery. The primary secondary battery technology today includes nickel-chromium batteries, nickel-hydrogen batteries, lead-acid batteries, lithium ion batteries, and the like. Nickel-chromium batteries and lead-acid batteries are early in appearance, but have the defects of low capacity and short service life, heavy metals in the batteries can cause huge pollution to the environment, and the development prospect is limited. Lithium ion batteries are the most widely used type of batteries at present, but at the same time, the demand for lithium is rapidly increased, the global lithium reserve is limited, the price is rapidly increased, the low-cost demand is not met, and the organic electrolyte used by the lithium ion batteries is inflammable, so that a great safety problem exists.
The aqueous zinc-based nickel-cobalt battery is a secondary battery which is raised in recent years, has higher battery capacity and longer service life compared with a nickel-chromium battery and a lead-acid battery, and does not have heavy metals and does not cause great harm to the environment. Compared with a lithium ion battery, the zinc storage is more abundant than lithium, the cost is much lower than that of the lithium ion battery, the electrolyte is aqueous solution of potassium hydroxide, combustion and explosion cannot be caused, the safety is relatively high, and the lithium ion battery has high potential value in the field of large-scale energy storage. The cobalt phosphate nano-sheet prepared by the hydrothermal method has large specific surface area, enhances ion accessibility, shortens an ion expansion path, accelerates electron conduction, leads to higher specific capacity, reduces surface capacity loss, and leads to longer cycle stability. Nickel and cobalt are all the fourth period elements in the periodic table, are adjacent in position and have similar atomic structures, and can be widely hypothesized that the nickel-cobalt doped positive electrode material can achieve the same or even better effect.
Disclosure of Invention
The invention aims to provide an aqueous zinc-based nickel-cobalt battery. The battery composition comprises a battery positive electrode material, a battery negative electrode material and an electrolyte solution. The positive electrode material of the battery is a nano flaky nickel cobalt phosphate composite material which uniformly grows on a three-dimensional substrate, and has the characteristics of rich raw materials, good stability, high specific capacity and the like. The method has mild reaction conditions and low cost, and can be applied to mass production. The cathode material of the battery is zinc sheet, and the electrolyte is potassium hydroxide with a certain concentration and soluble zinc salt aqueous solution, so that the problems of corrosion and passivation of the battery can be effectively prevented.
The water-based zinc-based nickel-cobalt battery comprises a battery anode material, a cathode material and electrolyte, wherein the anode material is nano-sheet nickel-cobalt phosphate which grows on a three-dimensional substrate, the cathode material is a zinc sheet, and the electrolyte comprises potassium hydroxide with a certain concentration and a soluble zinc salt aqueous solution.
The positive electrode material is nickel cobalt phosphate material, and the material is Ni x Co 3-x (PO 4 ) 2 Wherein x is more than or equal to 0 and less than or equal to 3.
The preparation method of the water-based zinc-based nickel-cobalt battery anode material comprises the following steps:
and (3) mixing cobalt (nickel) salt and phosphate at room temperature, dissolving in deionized water, transferring the obtained solution into a hydrothermal kettle containing a three-dimensional substrate material for hydrothermal reaction, taking out the foamed nickel after cooling, washing and drying to obtain the cobalt nickel phosphate material growing on the three-dimensional substrate.
The concentration of cobalt salt, nickel salt and phosphate used in the preparation of the positive electrode material is 0.0001-0.5 mol/L.
The cobalt salt used in the preparation of the positive electrode material comprises cobalt nitrate, cobalt chloride, cobalt sulfate or cobalt acetate. The nickel salt includes nickel nitrate, nickel chloride, nickel sulfate or nickel acetate.
The phosphate used in the preparation of the positive electrode material comprises ammonium dihydrogen phosphate, potassium dihydrogen phosphate or sodium dihydrogen phosphate.
The cobalt salt and the nickel salt used in the preparation of the positive electrode material are in any ratio.
The volume of the solution is 50% -90% of the volume of the high-pressure reaction kettle during preparation of the anode material.
The hydrothermal reaction temperature conditions of the invention are as follows: reacting for 1-36 h at 100-200 ℃.
The preparation method of the water-based zinc-based nickel-cobalt battery anode material comprises the steps of drying at 50-80 ℃ for 1-12 hours to obtain the water-based zinc-based nickel-cobalt battery anode material.
The three-dimensional substrate used in the preparation of the positive electrode material comprises any one of carbon paper, foam nickel, titanium alloy mesh or stainless steel mesh.
The negative electrode material is zinc sheet, zinc foil or zinc powder.
The electrolyte comprises potassium hydroxide with a certain concentration and soluble zinc salt.
The concentration of potassium hydroxide in the electrolyte is 0.1-10M.
The zinc salt in the electrolyte comprises zinc chloride, zinc sulfate, zinc nitrate or zinc acetate.
Compared with the prior art, the invention has the following advantages:
the water-based zinc-based nickel-cobalt battery consists of a battery anode, a battery cathode and an electrolyte. According to the invention, nickel cobalt phosphate is firstly applied to research of zinc-based nickel cobalt batteries, and the anode is a nano-sheet loaded nano-sheet nickel cobalt phosphate composite material which is uniformly grown on a three-dimensional substrate through a one-step hydrothermal method, so that the composite material has a larger specific surface area. The material has the advantages of abundant raw materials, good stability and high specific capacity, thereby showing excellent electrochemical performance. The nickel cobalt phosphate material disclosed by the invention has extremely high capacity, and the reduction peak-to-peak value can reach 100mA/cm at a certain sweeping speed 2 Above, and there is a continuous significant increase in the reduction peak to peak value as the concentration increases. The optimal composition ratio is found by adjusting the composition of nickel and cobalt, and the reduction peak value of the material can reach 350mA/cm 2 Above, the capacity of these peak transitions is much higher than the capacity of materials prepared by other processes in the same field.
Drawings
FIG. 1 shows that the reactant in example 1 is (a) Co 3 (PO 4 ) 2 -1（b）Co 3 (PO 4 ) 2 -2 SEM images of cobalt phosphate grown on a foamed nickel substrate under conditions.
FIG. 2 shows that the reactant in example 1 is (a) Co 3 (PO 4 ) 2 -1（b）Co 3 (PO 4 ) 2 -2 CV diagram of cobalt phosphate grown on foam nickel substrate under conditions.
FIG. 3 shows that in example 2 the reactant is Ni 3 (PO 4 ) 2 、CoNi 2 (PO 4 ) 2 、Co 1.5 Ni 1.5 (PO 4 ) 2 、Co 2 Ni(PO 4 ) 2 And Co 3 (PO 4 ) 2 -2 CV diagram of nickel cobalt phosphate grown on foam nickel substrate under conditions.
FIG. 4 is a diagram ofIn example 2, the reactant is Ni 3 (PO 4 ) 2 、CoNi 2 (PO 4 ) 2 、Co 1.5 Ni 1.5 (PO 4 ) 2 、Co 2 Ni(PO 4 ) 2 And Co 3 (PO 4 ) 2 -2 GCD plot of nickel cobalt phosphate grown on a foamed nickel substrate under conditions.
FIG. 5 is Co in example 2 1.5 Ni 1.5 (PO 4 ) 2 Stability diagram of the zinc-based nickel cobalt battery of the composition.
Detailed Description
The following examples are intended to further illustrate the invention, but not to limit it.
Example 1
Four parts of ammonium dihydrogen phosphate with a concentration of 1.2mM and 1.8mM of cobalt nitrate were dissolved in 80ml of deionized water, 0.01M and 0.05M urea were added respectively, and stirred at room temperature to obtain a pink solution, and the obtained solution was transferred to a solution containing nickel foam (2X 4cm 2 ) The hydrothermal reaction is carried out in the hydrothermal kettle, the temperature of the hydrothermal reaction is 120 ℃, the heat preservation time is 6 hours, after cooling, the foam nickel is taken out for washing for a plurality of times, and then the foam nickel is put into a 60 ℃ oven for drying. To obtain cobalt phosphate material (respectively marked as Co) growing on a foam nickel substrate 3 (PO 4 ) 2 -1 and Co 3 (PO 4 ) 2 -2）。
FIG. 1 (a) shows a cobalt phosphate sample Co obtained in example 1 of the present invention 3 (PO 4 ) 2 -SEM image of 1. As can be seen, the nano-sheet cobalt phosphate is successfully grown on the foam nickel substrate by a one-step hydrothermal method, and the nano-sheet structures can be uniformly and compactly arranged on the foam nickel. FIG. 1 (b) is a cobalt phosphate sample Co 3 (PO 4 ) 2 SEM images of-2, it can be seen that the morphology of fig. 1 (a) is still preserved and a layer of dense nanoparticles is again supported on the previous nanoplatelets.
FIG. 2 is a sample Co of cobalt phosphate in example 1 3 (PO 4 ) 2 -1 and Co 3 (PO 4 ) 2 Cyclic voltammogram of-2,it can be seen that the cobalt phosphate sample Co 3 (PO 4 ) 2 The redox peak of-2 increased to 160mA/cm compared to the base sample 2 . Reflecting the optimization of the urea added content control on the sample performance.
Example 2
Dissolving monoammonium phosphate with concentration of 1.2mM, nickel nitrate with concentration of 1.8mM and urea with concentration of 0.05M into 80ml deionized water, stirring at room temperature to obtain pink solution, and transferring the obtained solution into a solution containing foamed nickel (2 x 4 cm) 2 ) The hydrothermal reaction is carried out in the hydrothermal kettle, the temperature of the hydrothermal reaction is 120 ℃, the heat preservation time is 6 hours, after cooling, the foam nickel is taken out for washing for a plurality of times, and then the foam nickel is put into a 60 ℃ oven for drying. To obtain a cobalt phosphate material (marked as Ni) grown on a foam nickel substrate 3 (PO 4 ) 2 ）。
The method was modified as described above, with only cobalt nitrate adjusted to 0.6mM cobalt nitrate and 1.2mM nickel nitrate, to give a product of nickel cobalt phosphate material (labeled CoNi) grown on a foam nickel substrate 2 (PO 4 ) 2 ）。
The method is the same as the correction, only cobalt nitrate is adjusted to 0.9mM cobalt nitrate and 0.9mM nickel nitrate, and the obtained product is nickel cobalt phosphate material (marked as Co) growing on a foam nickel substrate 1.5 Ni 1.5 (PO 4 ) 2 ）。
The method is the same as the correction, only the cobalt nitrate is adjusted to 1.2mM cobalt nitrate and 0.6mM nickel nitrate, and the obtained product is nickel cobalt phosphate material (marked as Co) growing on a foam nickel substrate 2 Ni(PO 4 ) 2 ）。
FIG. 3 is a sample Ni of cobalt phosphate in example 2 3 (PO 4 ) 2 、CoNi 2 (PO 4 ) 2 、Co 1.5 Ni 1.5 (PO 4 ) 2 、Co 2 Ni(PO 4 ) 2 And Co in example 1 3 (PO 4 ) 2 The cyclic voltammogram of-2 shows that the ratio of different nickel to cobalt has great influence on the performance of the sample, wherein the sample has the best performance when the ratio of nickel to cobalt is 1:1, and the current density of a reduction peak can reach 380 mA/cm 2 。
FIG. 4 is a sample Ni of cobalt phosphate in example 2 3 (PO 4 ) 2 、CoNi 2 (PO 4 ) 2 、Co 1.5 Ni 1.5 (PO 4 ) 2 And Co 2 Ni(PO 4 ) 2 At 5mA/cm 2 The charge-discharge curve at current density shows that the reflected performance rule is consistent with FIG. 3, and is still Co 1.5 Ni 1.5 (PO 4 ) 2 The performance of the battery is best, and the time for one constant current charge and discharge can reach more than 5000 s.
FIG. 5 is a sample Co of the nickel cobalt phosphate of example 2 1.5 Ni 1.5 (PO 4 ) 2 The zinc-cobalt battery with the composition is 50mA/cm 2 Stability test chart at constant current of (2), it can be seen that the cobalt phosphate sample Co 1.5 Ni 1.5 (PO 4 ) 2 The coulomb efficiency is always close to one hundred percent in the 3000 charge-discharge process, which shows that the conversion efficiency in the reaction process is extremely high, and the capacity after 3000 cycles can still be kept above 65% of the initial capacity, so that the material has good cycle stability.

Claims (1)

1. The preparation method of the water-based zinc-based nickel-cobalt battery positive electrode material is characterized by comprising the following steps of:
dissolving monoammonium phosphate with concentration of 1.2mM, 0.9mM cobalt nitrate, 0.9mM nickel nitrate and 0.05M urea into 80ml deionized water, stirring at room temperature to obtain pink solution, and transferring into a solution containing foamed nickel 2 x 4cm 2 Carrying out hydrothermal reaction in a hydrothermal kettle, wherein the temperature of the hydrothermal reaction is 120 ℃, the heat preservation time is 6 hours, taking out foam nickel after cooling, washing for multiple times, and then drying in a 60 ℃ oven to obtain the cobalt phosphate material Co growing on the foam nickel substrate 1.5 Ni 1.5 (PO 4 ) 2 。
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CN114093679B (en) * 2021-11-29 2023-09-22 华中师范大学 beta-Ni (OH) grown in situ on large-size foam nickel 2 Nanosheet array electrode material and application thereof
CN114665088B (en) * 2022-03-08 2024-03-12 三峡大学 Preparation method of zinc cobalt nickel battery positive electrode composite material

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CN110767467A (en) * 2019-11-29 2020-02-07 桂林理工大学 NiCoZnP hollow microsphere material and preparation method thereof
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JP2013246983A (en) * 2012-05-25 2013-12-09 Sumitomo Metal Mining Co Ltd Method for manufacturing nickel-cobalt composite hydroxide
WO2016095669A1 (en) * 2014-12-17 2016-06-23 江苏合志锂硫电池技术有限公司 Preparation method for cobalt-nickel oxide electrode material
WO2018217274A1 (en) * 2017-05-24 2018-11-29 Nanotek Instruments, Inc. Alkali metal battery having a deformable quasi-solid electrode material
CN107337190A (en) * 2017-07-10 2017-11-10 佛山市利元合创科技有限公司 A kind of preparation method of the cobalt phosphate nickel grown in nickel foam of nano flower-like
CN110931769A (en) * 2019-11-27 2020-03-27 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of foamed nickel in-situ growth ternary cathode material, product and application
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CN111029160A (en) * 2019-12-24 2020-04-17 江苏理工学院 Zinc-cobalt double-metal selenide nanosheet electrode and preparation method thereof

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